CN110585864B - Reaction process suitable for low-temperature plasma concerted catalytic degradation of VOCs and membrane catalyst preparation process - Google Patents
Reaction process suitable for low-temperature plasma concerted catalytic degradation of VOCs and membrane catalyst preparation process Download PDFInfo
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- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
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- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/323—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 by electrostatic effects or by high-voltage electric fields
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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Abstract
The invention discloses a reaction process and a membrane catalyst preparation process suitable for low-temperature plasma concerted catalytic degradation of VOCs. The method comprises the steps of firstly carrying out anodic oxidation treatment on a TC4 titanium alloy electrode used for a low-temperature plasma device to enable the surface of the electrode to form a porous structure, then enabling a catalyst precursor to be attached to the surface of the electrode by using a coating method, finally assembling the electrode into a low-temperature plasma reactor, integrating the catalyst and the electrode through self high-voltage discharge of the reactor, and finally reacting with VOCs-containing waste gas. The exhaust gas in the electrode, due to the action of high and low pressure, will vibrate up and down, and this process increases the contact area between the gas and the catalyst. The invention effectively solves the problem of difficult catalyst filling in the plasma reaction device.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a reaction process and a membrane catalyst preparation process suitable for low-temperature plasma concerted catalytic degradation of VOCs.
Background
Along with the improvement of environmental awareness of people, the harm of Volatile Organic Compounds (VOCs) to the environment is more and more paid attention. The VOCs mostly refer to organic compounds with low boiling points and easy volatilization at normal temperature, and the common organic compounds comprise benzene, toluene, diethylbenzene, styrene, trichloroethylene, trichloromethane, trichloroethane, diisocyanatotoluene and the like, and are air pollutants with the environmental influence capability no less than PM 2.5. It is of various kinds and is easy to produce. Pollution emission of transportation means, industryThe exhaust gas produced by production, building decoration materials and the like contain a large amount of VOCs. And the VOCs are treated slowly due to the reasons of greatly influencing air quality, harming human health, influencing ozone layer and the like. At present, two processes, namely a combustion method and an adsorption method, are mainly used in China to treat VOCs. Wherein the combustion method comprises mixing VOCs with fuel to generate CO2、H2And O and the like. The process has obvious effect of treating VOCs and can convert toxic VOCs into inorganic matters with low toxicity. However, the process has the defects of higher treatment cost, unsuitability for treating a large amount of low-concentration polluted gas and the like. The adsorption method is to use porous medium, such as activated carbon, to adsorb harmful components in VOCs. The method has the advantages of simple and flexible operation, low medium cost, wide application range, better VOCs treatment effect, obvious treatment effect on a large amount of low-concentration pollution gas and the like. But the capacity of treating the medium with saturated adsorption is weaker at present, the adsorption effect of the medium is unstable, the maintenance cost is higher, and soil is easily polluted when the medium with saturated adsorption is buried, so that secondary pollution is caused.
The low-temperature plasma technology has become a leading-edge hotspot technology in the research field of VOCs treatment. Generally, it is believed that a series of complex physical and chemical reactions occur between high-energy electrons in the low-temperature plasma and the molecules of the VOCs, so that organic pollutants are degraded into non-toxic and harmless substances, O, OH generated by excitation of the high-energy electrons has strong oxidizability, and the molecules of the VOCs can be degraded into CO2And H2O, there are studies that suggest that atomic oxygen is the dominant influence of dissociation reactions that destroy VOCs. The method has simple equipment for treating the VOCs, has low requirement on the working environment, and is suitable for various places. However, the use of plasma only for processing VOCs often results in low energy utilization and the generation of toxic gases such as CO, which results in secondary pollution. Later researchers have proposed using catalysts in conjunction with plasmas to treat volatile organic gases, e.g. using MnO2The catalysts can reduce the activation energy of reactants, improve the energy efficiency, increase the selectivity of products and degrade CO generated in the reaction. Compared with the traditional low-temperature plasma methodThe daughter method indeed greatly improves the purification efficiency, but the existing filling type plasma synergistic catalyst mode has the main problems that the catalyst is inconvenient to fill and the gas resistance is large, so that the method is difficult to be applied to practice.
The invention provides a membrane catalyst which is prepared by taking TC4 titanium alloy as an electrode material of a plasma reaction device through an anodic oxidation method, active center immobilization and other modes and is used for the reaction of efficiently degrading VOCs (volatile organic compounds) by low-temperature plasma. The preparation method is convenient and efficient, and effectively solves the problem of difficult catalyst filling in a plasma reaction device.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a process suitable for the low-temperature plasma concerted catalytic degradation of VOCs. According to the method, a catalyst is not required to be filled under the coordination of low-temperature plasma, and the VOCs are degraded integrally and efficiently.
The invention aims at degrading VOCs, takes TC4 titanium alloy as an electrode material of a plasma reaction device, takes low-temperature plasma as a treatment mode, and is specifically realized by the following scheme:
putting a TC4 titanium alloy electrode (high-voltage and low-voltage electrodes) used for a low-temperature plasma device into an alkali solution, removing surface oil stains, and then sequentially washing the alkali solution with hot water and cold water;
fixing the deoiled TC4 titanium alloy electrode in an oxidation tank, adjusting the voltage to a certain value by taking 2mol/L sulfuric acid as electrolyte, and carrying out anodic oxidation to form a porous structure on the surface of the electrode; wherein the oxidation voltage is 60-150V;
dissolving a small amount of noble metal salt in tetrabutyl titanate solution to enable the noble metal salt to reach a certain concentration, and stirring at room temperature to slowly hydrolyze to form viscous glue solution; coating the glue solution on the surface of the electrode subjected to acid treatment in the step (2) to enable a catalyst precursor to be attached to the surface of the electrode, and drying;
the noble metal salt is silver nitrate or chloroplatinic acid, and the concentration is 0.001-0.2 mol/L;
the concentration of the tetrabutyl titanate solution is 50-300 g/L, and the solvent is ethanol;
and (4) assembling the electrodes in the step (3) into a low-temperature plasma reactor, and reacting for a period of time under certain discharge power through a specific plasma discharge mode in a hydrogen atmosphere to promote the decomposition of the catalyst precursor to obtain the required film catalyst.
The plasma discharge mode is glow discharge, dielectric barrier discharge, corona discharge or pulse discharge.
The discharge power is 2-10W, and the discharge time is 0.5-3 h.
And (5) continuously introducing waste gas containing 1000ppm of VOCs, and realizing efficient degradation of VOCs under the injection of 300J/L plasma energy.
The invention also aims to provide a preparation process of the membrane catalyst suitable for the low-temperature plasma concerted catalytic degradation of VOCs, which specifically comprises the following steps:
putting a TC4 titanium alloy electrode (high-voltage and low-voltage electrodes) used for a low-temperature plasma device into an alkali solution, removing surface oil stains, and then sequentially washing the alkali solution with hot water and cold water;
fixing the deoiled TC4 titanium alloy electrode in an oxidation tank, adjusting the voltage to a certain value by taking 2mol/L sulfuric acid as electrolyte, and carrying out anodic oxidation to form a porous structure on the surface of the electrode; wherein the oxidation voltage is 60-150V;
dissolving a small amount of noble metal salt in tetrabutyl titanate solution to enable the noble metal salt to reach a certain concentration, and stirring at room temperature to slowly hydrolyze to form viscous glue solution; coating the glue solution on the surface of the electrode subjected to acid treatment in the step (2) to enable a catalyst precursor to be attached to the surface of the electrode, and drying;
the noble metal salt is silver nitrate or chloroplatinic acid, and the concentration is 0.001-0.2 mol/L;
the concentration of the tetrabutyl titanate solution is 50-300 g/L, and the solvent is ethanol;
and (4) assembling the electrodes in the step (3) into a low-temperature plasma reactor, and reacting for a period of time under certain discharge power through a specific plasma discharge mode in a hydrogen atmosphere to promote the decomposition of the catalyst precursor to obtain the required film catalyst.
The plasma discharge mode is glow discharge, dielectric barrier discharge, corona discharge or pulse discharge.
The discharge power is 2-10W, and the discharge time is 0.5-3 h.
The specific principle of the invention is as follows: the method comprises the steps of firstly, carrying out anodic oxidation treatment on a TC4 titanium alloy electrode used for a low-temperature plasma device to enable the surface of the titanium alloy electrode to form a porous structure, then enabling a catalyst precursor to be attached to the surface of the electrode by using a coating method, finally assembling the electrode into a low-temperature plasma reactor, enabling the catalyst and the electrode to be integrated through self high-voltage discharge of the reactor, and finally reacting with VOCs-containing waste gas. The exhaust gas in the electrode, due to the action of high and low pressure, will vibrate up and down, and this process increases the contact area between the gas and the catalyst.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method is convenient and efficient, and can efficiently degrade VOCs;
(2) the invention effectively solves the problem of difficult catalyst filling in the plasma reaction device.
Detailed Description
The present invention is further analyzed with reference to the following embodiments.
Example 1
Firstly, placing a TC4 titanium alloy electrode used for a low-temperature plasma device in a NaOH solution with the mass content of 20%, removing surface oil stains, and then sequentially washing alkali liquor with hot water and cold water; fixing the deoiled TC4 titanium alloy electrode in an oxidation tank, adjusting the voltage to a certain value by taking 2mol/L sulfuric acid as electrolyte, preparing 100g/L tetrabutyl titanate mixed solution by using ethanol, dissolving a small amount of silver nitrate in the solution to enable the concentration of the silver nitrate solution to be 0.05mol/L, stirring at room temperature and slowly hydrolyzing to form viscous glue solution, coating the glue solution on the surface of the acid-treated electrode, drying, assembling the electrode into a low-temperature plasma reactor, turning on a plasma reaction power supply, and introducing H2By means of pulsesAnd (3) in a discharging mode, reacting the catalyst precursor for 0.5h under the condition that the discharging power is 2W to obtain the required film catalyst. Under the injection of plasma energy of 300J/L, VOCs with 1000ppm are introduced to simulate waste gas toluene for reaction. The effect of different voltage values on the degradation rate of VOCs is shown in table 1.
TABLE 1 Effect of different Voltage values on VOCs degradation Rate
| Voltage value (V) | VOCs degradation Rate (%) |
| 60 | 89 |
| 100 | 90 |
| 150 | 89 |
Example 2
Firstly, placing a TC4 titanium alloy electrode for a low-temperature plasma device in a NaOH solution with the mass content of 20%, removing surface oil stains, sequentially washing an alkali liquor by using hot water and cold water, fixing the deoiled titanium alloy in an oxidation tank, using 2mol/L sulfuric acid as an electrolyte, adjusting the voltage to 100V, preparing a mixed solution containing tetrabutyl titanate with a certain concentration by using ethanol, dissolving a small amount of silver nitrate in the solution to enable the concentration of the silver nitrate solution to be 0.05mol/L, stirring at room temperature and slowly hydrolyzing to form a viscous glue solution, coating the glue solution on the surface of the electrode subjected to acid treatment, drying, assembling the electrode into a low-temperature plasma reactor, turning on a plasma reaction power supply, and introducing H2By pulsed dischargeThe catalyst precursor is reacted for 0.5h under the condition that the discharge power is 2W to obtain the required film catalyst. Under the injection of plasma energy of 300J/L, VOCs with 1000ppm are introduced to simulate waste gas toluene for reaction. The effect of different concentrations of butyl titanate solutions on the degradation rate of VOCs is shown in table 2.
TABLE 2 influence of butyl titanate solutions of different concentrations on the degradation rate of VOCs
| Concentration of butyl titanate (g/L) | VOCs degradation Rate (%) |
| 50 | 87 |
| 150 | 90 |
| 300 | 90 |
Embodiment 3
Firstly, placing a TC4 titanium alloy electrode used for a low-temperature plasma device in NaOH solution with the mass content of 20%, removing surface oil stains, sequentially washing alkali liquor with hot water and cold water, fixing the deoiled titanium alloy in an oxidation tank, adjusting the voltage to 100V by using 2mol/L sulfuric acid as electrolyte, preparing tetrabutyl titanate mixed solution with the concentration of 100g/L with ethanol, dissolving a small amount of noble metal salt in the solution to ensure that the concentration of the noble metal salt solution is 0.05mol/L, stirring at room temperature and slowly hydrolyzing to form viscous glue solution, coating the glue solution on the surface of the electrode subjected to acid treatment, drying, assembling the electrode into a low-temperature plasma reactor, turning on a plasma reaction power supply, and introducing a plasma reaction power supplyH2And reacting the catalyst precursor for 0.5h under the condition of the discharge power of 2W by using a pulse discharge mode to obtain the required membrane catalyst. Under the injection of plasma energy of 300J/L, VOCs with 1000ppm are introduced to simulate waste gas toluene for reaction. The effect of different kinds of noble metal salt solutions on the degradation rate of VOCs is shown in table 3.
TABLE 3 influence of different kinds of noble metal salt solutions on the degradation rate of VOCs
| Noble metal salt species | VOCs degradation Rate (%) |
| Silver nitrate | 90 |
| Chloroplatinic acid | 88 |
Example 4
Firstly, placing a TC4 titanium alloy electrode for a low-temperature plasma device in a NaOH solution with the mass content of 20%, removing surface oil stains, sequentially washing alkali liquor with hot water and cold water, fixing the deoiled titanium alloy in an oxidation tank, taking 2mol/L sulfuric acid as electrolyte, adjusting the voltage to 100V, preparing a tetrabutyl titanate mixed solution with the concentration of 100g/L with ethanol, dissolving silver nitrate with a certain concentration in the solution, stirring at room temperature and slowly hydrolyzing to form a viscous glue solution, coating the glue solution on the surface of the acid-treated electrode, drying, assembling the electrode into a low-temperature plasma reactor, turning on a plasma reaction power supply, introducing H, and performing secondary oxidation to obtain the low-temperature plasma reactor2And reacting the catalyst precursor for 0.5h under the condition of the discharge power of 2W by using a pulse discharge mode to obtain the required membrane catalyst. At 300J/LAnd introducing VOCs (volatile organic compounds) containing 1000ppm to simulate waste gas toluene to react under the injection of plasma energy. The effect of different concentrations of silver nitrate solutions on the degradation rate of VOCs is shown in table 4.
TABLE 4 Effect of silver nitrate solutions of different concentrations on VOCs degradation Rate
| Silver nitrate solution concentration (mol/L) | VOCs degradation Rate (%) |
| 0.001 | 84 |
| 0.050 | 90 |
| 0.100 | 92 |
| 0.200 | 92 |
Example 5
Firstly, placing a TC4 titanium alloy electrode used for a low-temperature plasma device in NaOH solution with the mass content of 20%, removing surface oil stains, sequentially washing alkali liquor by hot water and cold water, fixing the deoiled titanium alloy in an oxidation tank, adjusting the voltage to 100V by using 2mol/L sulfuric acid as electrolyte, preparing tetrabutyl titanate mixed solution with the concentration of 100g/L by using ethanol, dissolving a small amount of silver nitrate in the solution to ensure that the concentration of the silver nitrate solution is 0.05mol/L, stirring at room temperature and slowly hydrolyzing to form viscous glue solution, coating the glue solution on the surface of the electrode subjected to acid treatment, drying, and assembling the electrode into a low-temperature plasma reactor,turning on plasma reaction power supply and introducing H2And reacting the catalyst precursor for 0.5h under the condition of the discharge power of 2W by using a certain discharge mode to obtain the required membrane catalyst. Under the injection of plasma energy of 300J/L, VOCs with 1000ppm are introduced to simulate waste gas toluene for reaction. The effect of different discharge patterns on the degradation rate of VOCs is shown in table 5.
TABLE 5 Effect of different discharge modes on VOCs degradation Rate
| Discharge mode | VOCs degradation Rate (%) |
| Glow discharge | 80 |
| Dielectric barrier discharge | 93 |
| Corona discharge | 85 |
| Pulse discharge | 90 |
Example 6
Firstly, placing a TC4 titanium alloy electrode for a low-temperature plasma device in a NaOH solution with the mass content of 20%, removing surface oil stains, sequentially washing an alkali liquor by using hot water and cold water, fixing the deoiled titanium alloy in an oxidation tank, adjusting the voltage to 100V by using 2mol/L sulfuric acid as an electrolyte, preparing a tetrabutyl titanate mixed solution with the concentration of 100g/L by using ethanol, and dissolving a small amount of silver nitrate in the solution to dissolve the silver nitrateThe concentration of the solution is 0.05mol/L, the solution is stirred at room temperature and slowly hydrolyzed to form viscous glue solution, then the glue solution is coated on the surface of an acid-treated electrode, the electrode is dried, then the electrode is assembled into a low-temperature plasma reactor, a plasma reaction power supply is turned on, and H is introduced2And reacting the catalyst precursor for 0.5h under certain discharge power by using a pulse discharge mode to obtain the required membrane catalyst. Under the injection of plasma energy of 300J/L, VOCs with 1000ppm are introduced to simulate waste gas toluene for reaction. The effect of different discharge powers on the degradation rate of VOCs is shown in table 6.
TABLE 6 Effect of different discharge powers on VOCs degradation Rate
| Discharge power (W) | VOCs degradation Rate (%) |
| 2 | 90 |
| 5 | 96 |
| 10 | 98 |
Example 7
Firstly, placing a TC4 titanium alloy electrode for a low-temperature plasma device in a NaOH solution with the mass content of 20%, removing surface oil stains, sequentially washing an alkali liquor by using hot water and cold water, fixing the deoiled titanium alloy in an oxidation tank, adjusting the voltage to 100V by using 2mol/L sulfuric acid as an electrolyte, preparing a tetrabutyl titanate mixed solution with the concentration of 100g/L by using ethanol, and dissolving a small amount of silver nitrate in the solution to ensure that the concentration of a silver nitrate solution is 0.05moL/L, stirring at room temperature, slowly hydrolyzing to obtain viscous liquid, coating the liquid on the surface of acid-treated electrode, drying, assembling the electrode into low-temperature plasma reactor, turning on the plasma reaction power supply, and introducing H2And reacting the catalyst precursor for a certain time under the condition of the discharge power of 2W by using a pulse discharge mode to obtain the required membrane catalyst. Under the injection of plasma energy of 300J/L, VOCs with 1000ppm are introduced to simulate waste gas toluene for reaction. The effect of different reaction times on the degradation rate of VOCs is shown in table 7.
TABLE 7 Effect of different reaction durations on VOCs degradation Rate
| Length of reaction (h) | VOCs degradation Rate (%) |
| 0.5 | 90 |
| 2 | 92 |
| 3 | 92 |
Example 8
Firstly, placing a TC4 titanium alloy electrode for a low-temperature plasma device in a NaOH solution with the mass content of 20%, removing surface oil stains, sequentially washing an alkali liquor by using hot water and cold water, fixing the deoiled titanium alloy in an oxidation tank, adjusting the voltage to 100V by using 2mol/L sulfuric acid as an electrolyte, preparing a tetrabutyl titanate mixed solution with the concentration of 100g/L by using ethanol, and dissolving a small amount of silver nitrate in the solution to ensure that the concentration of a silver nitrate solution is 0.05molL, stirring at room temperature, hydrolyzing slowly to obtain viscous liquid, coating the liquid on the surface of acid-treated electrode, drying, assembling the electrode into low-temperature plasma reactor, turning on the plasma reaction power supply, and introducing H2And reacting the catalyst precursor for 0.5h under the condition of the discharge power of 2W by using a pulse discharge mode to obtain the required membrane catalyst. Under the injection of plasma energy of 300J/L, simulated waste gas containing 1000ppm of different types of VOCs is introduced for reaction. The degradation of different types of VOCs during discharge is shown in table 8.
TABLE 8 degradation of different VOCs during discharge
| Gas species | VOCs degradation Rate (%) |
| Toluene | 90 |
| Acetone (II) | 93 |
| Ethanol | 98 |
| Ethyl acetate | 95 |
| N-hexane | 85 |
Claims (10)
1. A membrane catalyst preparation process suitable for a reaction of degrading VOCs by low-temperature plasma concerted catalysis is characterized by comprising the following steps:
putting a TC4 titanium alloy electrode used for a low-temperature plasma device into an alkali solution, removing surface oil stains, and then sequentially washing the alkali solution with hot water and cold water;
fixing the deoiled titanium alloy in an oxidation tank, regulating the voltage to 60-150V by taking sulfuric acid as electrolyte, and carrying out anodic oxidation to form a porous structure on the surface of an electrode;
dissolving a small amount of noble metal salt in tetrabutyl titanate solution, stirring at room temperature, and slowly hydrolyzing to form viscous glue solution; coating the glue solution on the surface of the electrode subjected to acid treatment in the step (2) to enable a catalyst precursor to be attached to the surface of the electrode, and drying;
step (4), assembling the electrodes in the step (3) into a low-temperature plasma reactor, and reacting for a period of time under certain discharge power through a specific plasma discharge mode in a hydrogen atmosphere to promote the decomposition of a catalyst precursor to obtain a required membrane catalyst;
the plasma discharge mode is glow discharge, dielectric barrier discharge, corona discharge or pulse discharge;
the discharge power is 2-10W.
2. The process for preparing a membrane catalyst according to claim 1, wherein the sulfuric acid concentration in the step (2) is 2 mol/L.
3. The process for preparing a membrane catalyst according to any one of claims 1 to 2, wherein the concentration of tetrabutyl titanate in the step (3) is 50 to 300 g/L.
4. The process for preparing a membrane catalyst according to any one of claims 1 to 2, wherein the noble metal salt in the step (3) is silver nitrate or chloroplatinic acid, and the concentration is 0.001 to 0.2 mol/L.
5. The process for preparing a membrane catalyst according to any one of claims 1 to 2, wherein the discharge time in the step (4) is 0.5 to 3 hours.
6. The reaction process suitable for the low-temperature plasma concerted catalytic degradation of VOCs is characterized by comprising the following steps:
putting a TC4 titanium alloy electrode used for a low-temperature plasma device into an alkali solution, removing surface oil stains, and then sequentially washing the alkali solution with hot water and cold water;
fixing the deoiled titanium alloy in an oxidation tank, regulating the voltage to 60-150V by taking sulfuric acid as electrolyte, and carrying out anodic oxidation to form a porous structure on the surface of an electrode;
dissolving a small amount of noble metal salt in tetrabutyl titanate solution, stirring at room temperature, and slowly hydrolyzing to form viscous glue solution; coating the glue solution on the surface of the electrode subjected to acid treatment in the step (2) to enable a catalyst precursor to be attached to the surface of the electrode, and drying;
step (4), assembling the electrodes in the step (3) into a low-temperature plasma reactor, and reacting for a period of time under certain discharge power through a specific plasma discharge mode in a hydrogen atmosphere to promote the decomposition of a catalyst precursor to obtain a required membrane catalyst;
the plasma discharge mode is glow discharge, dielectric barrier discharge, corona discharge or pulse discharge;
the discharge power is 2-10W;
and (5) continuously introducing waste gas containing 1000ppm of VOCs, and realizing efficient degradation of VOCs under the injection of 300J/L plasma energy.
7. The process according to claim 6, wherein the concentration of sulfuric acid in step (2) is 2 mol/L.
8. The process according to any one of claims 6 to 7, wherein the concentration of tetrabutyl titanate in the step (3) is 50-300 g/L.
9. The reaction process suitable for the low-temperature plasma concerted catalytic degradation of VOCs according to any one of claims 6 to 7, characterized in that the noble metal salt in the step (3) is silver nitrate or chloroplatinic acid, and the concentration is 0.001-0.2 mol/L.
10. The reaction process suitable for the low-temperature plasma concerted catalytic degradation of VOCs according to any one of claims 6 to 7, wherein the discharge time in the step (4) is 0.5-3 h.
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